Single‐atom M‒N‒C catalysts have attracted tremendous attention for their application to electrocatalysis. Nitrogen‐coordinated mononuclear metal moieties (MNx moities) are bio‐inspired active sites ...that are analogous to various metal‐porphyrin cofactors. Given that the functions of metal‐porphyrin cofactors are highly dependent on the local coordination environments around the mononuclear active site, engineering MNx active sites in heterogeneous M‒N‒C catalysts would provide an additional degree of freedom for boosting their electrocatalytic activity. This work presents a local coordination structure modification of FeN4 moieties via morphological engineering of graphene support. Introducing highly wrinkled structure in graphene matrix induces nonplanar distortion of FeN4 moieties, resulting in the modification of electronic structure of mononuclear Fe. Electrochemical analysis combined with first‐principles calculations reveal that enhanced electrocatalytic lithium polysulfide conversion, especially the Li2S redox step, is attributed to the local structure modified FeN4 active sites, while increased specific surface area also contributes to improved performance at low C‐rates. Owing to the synergistic combination of atomic‐level modified FeN4 active sites and morphological advantage of graphene support, Fe‒N‒C catalysts with wrinkled graphene morphology show superior lithium–sulfur battery performance at both low and high C‐rates (particularly 915.9 mAh g−1 at 5 C) with promising cycling stability.
Atomic‐level engineering of MNx active sites is a desirable strategy to enhance and fine‐tune electrocatalytic performance of M‒N‒C catalysts. FeN4 active sites on wrinkled graphene support exhibits different structural and electronic properties compared to square‐planar FeN4 moieties. The synergistic combination of modified FeN4 active sites and morphological advantage of wrinkled graphene support improves the electrocatalytic performance for lithium–sulfur conversion chemistry.
The quantitative label-free detection of neurotransmitters provides critical clues in understanding neurological functions or disorders. However, the identification of neurotransmitters remains ...challenging for surface-enhanced Raman spectroscopy (SERS) due to the presence of noise. Here, we report spread spectrum SERS (ss-SERS) detection for the rapid quantification of neurotransmitters at the attomolar level by encoding excited light and decoding SERS signals with peak autocorrelation and near-zero cross-correlation. Compared to conventional SERS measurements, the experimental result of ss-SERS shows an exceptional improvement in the signal-to-noise ratio of more than three orders of magnitude, thus achieving a high temporal resolution of over one hundred times. The ss-SERS measurement further allows the attomolar SERS detection of dopamine, serotonin, acetylcholine, γ-aminobutyric acid, and glutamate without Raman reporters. This approach opens up opportunities not only for investigating the early diagnostics of neurological disorders or highly sensitive biomedical SERS applications but also for developing low-cost spectroscopic biosensing applications.
Compared to nanostructured platinum (Pt) catalysts, ordered Pt-based intermetallic nanoparticles supported on a carbon substrate exhibit much enhanced catalytic performance, especially in fuel cell ...electrocatalysis. However, direct synthesis of homogeneous intermetallic alloy nanocatalysts on carbonaceous supports with high loading is still challenging. Herein, we report a novel synthetic strategy to directly produce highly dispersed MPt alloy nanoparticles (M = Fe, Co, or Ni) on various carbon supports with high catalyst loading. Importantly, a unique bimetallic compound, composed of M(bpy)32+ cation (bpy = 2,2′-bipyridine) and PtCl62– anion, evenly decomposes on carbon surface and forms uniformly sized intermetallic nanoparticles with a nitrogen-doped carbon protection layer. The excellent oxygen reduction reaction (ORR) activity and stability of the representative reduced graphene oxide (rGO)-supported L10-FePt catalyst (37 wt %-FePt/rGO), exhibiting 18.8 times higher specific activity than commercial Pt/C catalyst without degradation over 20 000 cycles, well demonstrate the effectiveness of our synthetic approach toward uniformly alloyed nanoparticles with high homogeneity.
Graphene‐based magnetic materials exhibit novel properties and promising applications in the development of next‐generation spintronic devices. Modern synthesis techniques have paved the way to ...design precisely the local environments of metal atoms anchored onto a nitrogen‐doped graphene matrix. Herein, it is demonstrated that grafting cobalt (Co) into the graphene lattice induces robust and stable room‐temperature ferromagnetism. These comprehensive experiments and first‐principles calculations unambiguously identify that the mechanism for this unusual ferromagnetism is π‐d orbital hybridization between Co dxz and graphene pz orbitals. Here, it is found that the magnetic interactions of Co–carbon ions are mediated by the spin‐polarized graphene pz orbitals, and room temperature ferromagnetism can be stabilized by electron doping. It is also found that the electronic structure near the Fermi level, which sets the nature of spin polarization of graphene pz bands, strongly depends on the local environment of the Co moiety. This is the crucial, previously missing, ingredient that enables control of the magnetism. Overall, these observations unambiguously reveal that engineering the atomic structure of metal‐embedded graphene lattices through careful d to p orbital interactions opens a new window of opportunities for developing graphene‐based spintronics devices.
Graphene is a promising candidate for application in spintronic devices and quantum computation. Herein, it is demonstrated that Co grafted graphene shows robust room temperature ferromagnetism via Co dxz and graphene pz orbital hybridization. It is also identified that the origin behind the magnetic interaction of Co‐C ions is mediated by spin polarized graphene pz orbitals, and the room temperature ferromagnetism can be stabilized by electron doping.
Advent and fast spread of pandemic diseases draw worldwide attention to rapid, prompt, and accurate molecular diagnostics with technical development of ultrafast polymerase chain reaction (PCR). ...Microfluidic on-chip PCR platforms provide highly efficient and small-volume bioassay for point-of-care diagnostic applications. Here we report ultrafast, real-time, and on-chip nanoplasmonic PCR for rapid and quantitative molecular diagnostics at point-of-care level. The plasmofluidic PCR chip comprises glass nanopillar arrays with Au nanoislands and gas-permeable microfluidic channels, which contain reaction microchamber arrays, a precharged vacuum cell, and a vapor barrier. The on-chip configuration allows both spontaneous sample loading and microbubble-free PCR reaction during which the plasmonic nanopillar arrays result in ultrafast photothermal cycling. After rapid sample loading less than 3 min, two-step PCR results for 40 cycles show rapid amplification in 264 s for lambda-DNA, and 306 s for plasmids expressing SARS-CoV-2 envelope protein. In addition, the in situ cyclic real-time quantification of amplicons clearly demonstrates the amplification efficiencies of more than 91%. This PCR platform can provide rapid point-of-care molecular diagnostics in helping slow the fast-spreading pandemic.
Biological wonders, found in insects such as antireflecting moth eyes, compound eyes in a honey bee, firefly lanterns, and iridescent butterfly wings, inspire human beings for advanced light imaging ...and illumination technologies. Dazzling advances of micro‐ and nanofabrication technologies allow insect‐inspired structures, for example, artificial compound eyes with a wide field of view and low aberration, bioinspired light‐emitting diode lenses, and structural coloration templates, featuring miniaturization. Besides, plasmonics and metamaterials offer an unprecedented approach that overcomes the diffraction limit and unveils unknown optical phenomena in ultrastructures inspired by insects. Here, insect‐inspired photonic structures for light imaging, light extraction, and structural coloration are reviewed, and photonic functions and structure fabrications inspired by insects that can be applied in advanced imaging and illumination applications are discussed.
Biological marvels, found in insects such as compound eyes and firefly lanterns, inspire human beings for advanced light imaging and illumination technologies. This article focuses on recent progress of photonic micro/nano structures inspired from insect smartness regarding with functions and fabrication methods. In addition, perspectives and prospects using plasmonics and metamaterials for insect inspired photonics are discussed.
Emerging molecular diagnosis requires ultrafast polymerase chain reaction (PCR) on chip for rapid precise detection of infectious diseases in the point-of-care test. Here, we report nanoplasmonic ...on-chip PCR for rapid precision molecular diagnostics. The nanoplasmonic pillar arrays (NPA) comprise gold nanoislands on the top and sidewall of large-scale glass nanopillar arrays. The nanoplasmonic pillars enhance light absorption of a white light-emitting diode (LED) over the whole visible range due to strong electromagnetic hotspots between the nanoislands. As a result, they effectively induce photothermal heating for ultrafast PCR thermal cycling. The temperature profile of NPA exhibits 30 cycles between 98 and 60 °C for a total of 3 min and 30 s during the cyclic excitation of white LED light. The experimental results also demonstrate the rapid DNA amplification of both 0.1 ng μL–1 of λ-DNA in 20 thermal cycles and 0.1 ng μL–1 of complementary DNA of Middle East respiratory syndrome coronavirus in 30 thermal cycles using a conventional PCR volume of 15 μL. This nanoplasmonic PCR technique provides a new opportunity for rapid precision molecular diagnostics.
Crystalline poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) nanofibrils with an electrical conductivity of 4380 S cm‐1 are formed via a solution process using H2SO4. The ...concentrated H2SO4 treatment induces a significant structural rearrangement of the PEDOT:PSS via a charge‐separated transition mechanism, resulting in highly ordered and densely packed PEDOT:PSS nanofibrils. The PEDOT:PSS electrode shows a sheet resistance of 46 Ω sq‐1 with 90% optical transmittance.
Visible-light-driven organic transformations are of great interest in synthesizing valuable fine chemicals under mild conditions. The merger of heterogeneous photocatalysts and transition metal ...catalysts has recently drawn much attention due to its versatility for organic transformations. However, these semi-heterogenous systems suffered several drawbacks, such as transition metal agglomeration on the heterogeneous surface, hindering further applications. Here, we introduce heterogeneous single Ni atoms supported on carbon nitride (NiSAC/CN) for visible-light-driven C-N functionalization with a broad substrate scope. Compared to a semi-heterogeneous system, high activity and stability were observed due to metal-support interactions. Furthermore, through systematic experimental mechanistic studies, we demonstrate that the stabilized single Ni atoms on CN effectively change their redox states, leading to a complete photoredox cycle for C-N coupling.
In this work, the first demonstration of heterogeneous photoredox C-N coupling is reported using Ni atoms on C
3
N
4
. Due to metal-support interactions, high activity and stability were observed during visible-light-driven C-N functionalization.
To understand the effects rendered on the relevant basic physical properties and device function by controlling the regiochemistry of the ...cyclopenta1,2‐b:5,4‐b′dithiophene‐fluorobenzoc1,2,5thiadiazole polymer (hereafter referred to as the CDT‐FBT polymer), two polymers, the regiorandom polymer (RA) and regioregular version (RR), respectively, are synthesized and characterized. In addition, an efficient route for synthesizing a key monomer for RR using various synthesis scope and optimizing the reaction conditions is discussed. Although RA exhibits optical, electrochemical, and morphological properties similar to RR, it shows better field‐effect transistor (FET) performance. Surprisingly, by employing a capillarity‐mediated sandwich‐casting process on a nanogrooved substrate, an unprecedented mobility of 17.8 cm2 V−1 s−1 is obtained for RA‐based FETs; this mobility value is almost twofold greater than those of the corresponding RR‐based FETs. For the first time, this study challenges previously reported results in that high carrier mobility is related to the high degree of polymer order induced by the backbone regioregularity.
Organic field‐effect transistors: Two polymers, a regiorandom polymer (RA) and a regioregular version (RR), have been synthesized and characterized. An unprecedented mobility of 17.8 cm2 V−1 s−1 was obtained for RA‐based field‐effect transistors (FETs). The high carrier mobility is related to the high degree of polymer order induced by backbone regioregularity.
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